In‐Situ Derived Defective Ru Particles Anchored on Ru–Ni Layered Double Hydroxides for Enhanced Alkaline Hydrogen Evolution

Abstract Developing active, stable, and cost‐efficient electrocatalysts to replace platinum for the alkaline hydrogen evolution reaction (HER) is highly desirable yet represents a great challenge. Here, it is reported on a facile one‐pot synthesis of Ru _x Ni layered double hydroxides (Ru _x Ni‐LDHs) that exhibit remarkable HER activity and stability after an in‐situ activation treatment, surpassing most state‐of‐the‐art Ru‐based catalysts as well as commercial Ru/C and Pt/C catalysts. The structural and chemical changes triggered by in‐situ activation are systematically investigated, and the results clearly show that the pristine, less‐active Ru _x Ni‐LDHs are transformed into a highly active catalyst characterized by raft‐like, defect‐rich Ru° particles decorated on the surface of Ru _x Ni‐LDHs. Density functional theory (DFT) calculations reveal that the defective Ru sites can effectively optimize the reaction pathway and lower the free energies of the elemental steps involved, leading to enhanced intrinsic activity. This work highlights the importance of the currently understudied strategy of defect engineering in boosting the HER activity of Ru‐based catalysts and offers an effective approach involving in‐situ electrochemical activation for the development of high‐performance alkaline HER catalysts.